The increasing use of Metal-Organic Frameworks (MOFs) in separation, catalysis, or storage is linked to the targeted modification of their composition or porosity metrics. While modification of pore shape and size necessarily implies the assembly of alternative nets, compositional changes often rely on postsynthetic modification adapted to the functionalization or exchange of the organic linker or the modification of the inorganic cluster by metal exchange methods. We describe an alternative methodology that enables the integration of both types of modification, structural and compositional, in titanium MOFs by metal exchange reaction of the heterometallic cluster TiCa.
View Article and Find Full Text PDFReticular chemistry has in the post-synthetic modification (PSM) of frameworks one of the most versatile tools to adapt the systems' physicochemical properties to the specific requirements which are imposed by their application in different contexts. We can safely say that PSM methodologies in all their variants are currently one of the main resources that reticular chemists turn to when they need to diversify a framework compositionally. Practically all these modifications require the integration of functional groups appended to the organic linkers in the framework, either by direct synthesis or by post-synthetic exchange.
View Article and Find Full Text PDFTitanium-organic frameworks offer distinctive opportunities in the realm of metal-organic frameworks (MOFs) due to the integration of intrinsic photoactivity or redox versatility in porous architectures with ultrahigh stability. Unfortunately, the high polarizing power of Ti cations makes them prone to hydrolysis, thus preventing the systematic design of these types of frameworks. We illustrate the use of heterobimetallic cluster TiCa as a persistent building unit compatible with the isoreticular design of titanium frameworks.
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